Composition for dyeing human hair

ABSTRACT

Composition for dyeing human hair in rich, colorful tones. The dyes consist of a surfactant with a hair coloring agent which may be 6-(2-aminoethylamino)-1,2,3,4-tetrahydronaphtho-(2,3-f)quinoxaline-7,12 -dione; 6-(2-methyl-aminoethylamino)-4-methyl1,2,3,4-tetrahydronaphtho-(2,3-f) -quinoxaline-7,12-dione; and 6(2-ethylaminoethylamino)-4-ethyl-1,2,3,4-tetrahydronaphtho-(2,3f) -quinoxaline-7,12-dione or mixtures of such coloring agents.

I United States Patent [151 3,661,500 Dehn, Jr. et al. 5] May 9, 1972[54] COMPOSITION FOR DYEING HUMAN Primary Examiner-George F. Lesmes HAIRAssistant Examiner-Patricia C. Ives Attorney-Frank M. Nolan [72]Inventors: Joseph W. Dehn, Jr., Great Neck, N.Y.;

Mary R. Paradiso, Clifton, NJ.

[T-n'] Assignee: Shulton, Inc., Clifton, NJ. ABSTRACT [22} Flled: July1970 Composition for dyeing human hair in rich, colorful tones. [2]}Appl. No.: 64,871 The dyes consist of a surfactant with a hair coloringagent which may be 6( Z-aminoethylamino )-1 ,2,3,4-tetrahydronaphtho-[2,3-f1-quinoxaline-7,12-dione; 6-( 2- [52] CI...8/10, 8/17, 260/268 PC h i i 4 1 2 3 4 [51] Int.Cl. ..D06p 3/04 2 34 712 and 2 Field Of Search 260/268 378 ethylaminoethylamino)-4-ethyl-l,2,3,4-tetrahydronaphtho- [2,3-fJ-quinoxaline-7,l2-dione or mixtures ofsuch coloring [56] References Cited agents.

FOREIGN PATENTS OR APPLICATIONS 1/1969 Netherlands ..260/268 PC 8Claims, No Drawings COMPOSITION FOR DYEING HUMAN HAIR This inventionrelates to compositions for dyeing keratinous fibers and particularlyfor dyeing human hair. The compositions of this invention comprise anactive dye material selected from the class consisting of6-(2-aminoethylamino)- 1,2,3 ,4-tetrahy-dronaphtho-l2,3-f]-quinoxaline-7, l 2-dione; 6-( Z-methylamino-ethylamino)-4-methyl-l ,2,3,4- tetrahydronaphtho-[2,3-f1-quinoxaline-7,l2'dione;and 6-(2- ethylaminoethylamino)-4-ethyl-1,2,3,4--tetrahydronaphtho-[2,3-f]-quinoxaline-7,12-dione and a surfactand. Desirably there arealso added a thickening agent and a basic or acidic agent for regulatingthe pH of the composition. The surfactant is conveniently 0.1 toIOpercent, desirably 0.2 to 5 percent and preferably 0.5 to 2 percent ofthe weight of the composition, while conveniently, the thickening agentis 0.1 to percent, desirably 0.2 to 5 percent and preferably 0.5 to 2percent of the weight of the composition. While the pH of thecomposition may vary over a wide range, a range of 6 to 10 is desirable.

The active dye employed in the composition of this invention is asubstituted anthraquinone having the formula:

H CH2 in which R is hydrogen, methyl or ethyl.

The substitutedl,2,3,4-tetrahydronaphtho-[2,3-f]-quinoxaline-7,l2-diones employed asthe active dyes may be produced by reacting, leucoquinizarin with adiamine having the formula: Y

H NCl-l -CH,NHR (2) The reactants are heated at 100 C under anatmosphere of nitrogen. Subsequently, air is permitted to oxidize theleuco moiety of the product. The reaction which takes place is indicatedby the following:

H l H I n 2H,N cm01n-NHR I H 1. At 100 under N2 Y I \H Subsequently 2.Air oxidize the leuco O 011 of the product Leucoquinizarin 1! CE: 0 UNC] l: H l

yethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,polyoxyethylene sorbitan monooleate, cetyl pyridinium bromide, cetylpyridinium chloride, stearyl dimethyl benzyl ammonium chloride, anddodecyl benzyl dimethyl ammonium chloride.

Examples of thickening agents are hydroxyethylcellulose,methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose,sodium alginate, gum arabic, and polyacrylic acid sodium salt.

The compositions are conveniently dissolved in a solvent such as water,ethyl alcohol, isopropyl alcohol, propylene glycol and triethyleneglycol.

Dyes employed in conjunction with the active dyes of the compositions ofthis invention are any other dyes normally used in the dyeing of humanhair, including nitro, azo, or quinone types. Examples of dyes which maybe used are: 2-nitro-pphenylenediamine, 4-nitro-m-phenylenediamine,4-nitro-o phenylenediamine and various mono, di and tri-N-substitutedderivatives of these three dyes.

Other examples include: 5-nitro-2,4-diaminotoluene, 4-nitro-2-aminophenol, isopicramic acid, N-methyl isopicramic acid,Z-hydroxyl ,4-naphthoquinone, 5-hydroxy-1,4- naphthoquinone,2,4-.dinitro-4'-hydroxy-diphenylamine, 2,4-dinitro-4'-amino-diphenylamine, and 3-(m-nitrophenylazo)-2,4-dihydroxy-1-methyl quinoline.

A more comprehensive understanding of this invention is obtained byreference to the following examples.

The mixture had a pH of 9.5 The color on white hair was light goldenbrown.

The active dye which is 6-(2-aminoethylamino)-l ,2,3,4-tetrahydronaphtho-[2,3-f1-quinoxaline-7,l2-dione may be prepared byeither of the following procedures:

PROCEDURE I 19.2 G (0.08 mole) of leucoquinizarin was added to ml ofethylenediamine under a nitrogen atmosphere at below 40 C. The reactionwas then heated and stirred at 100 C for 50 minutes. lt was subsequentlyoxidized by bubbling in air for 30 minutes. After cooling and standingovernight the resulting precipitate was filtered, washed first withdiethyl ether and then with hot methyl alcohol and dried to give 10.8 g(0.0335 mole) of solid product equal to 41.9 percent of theory. Thismaterial was recrystallized from n-butyl alcohol to produce 7.4 g (0.023mole) of crystals with m.p. 207-208 C equivalent to 27.8 percent of thetheoretical quantity of 6-( 2- aminoethylamino)-l,2,3,4-tetrahydronaphtho-[ 2,3-f1-quinoxaline-7,l 2-dione.

PROCEDURE ll 19.2 G (0.08 mole) of leucoquinizarin was mixed with 100 mlof ethylenediamine and a thick purple mass formed. The reaction washeated at 100 C for 1 hour. Subsequently air was bubbled through tooxidize the leuco. After standing overnight at room temperature, thecrystalline product which had separated was filtered, washed with asmall amount of ether and hot methyl alcohol and dried. The product wasthen recrystallized from n-butyl alcohol to give 3.6 g (0.01 l 1 mole)of black crystals a copper reflex with m.p. 207208 C equal to. 13.9percent of theoretical yield of 6-(2- aminoethylamino )-1,2,3,4-tetrahydronaphtho-[ 2,3-f]-quinoxaline-7,12-dione. A second cropof 3.5 g was isolated and then recrystallized from n-butyl alcohol togive another 2.8 g (0.00864 mole) of crystals with m.p. 207208 C equalto a 10.8 percent yield. The total yield of product was 6.4 g (0.01975mole) or 24.7 percent of theory yield after recrystallization.

The 2,3-dihydro-l,4-dihydroxyanthraquinone (leucoquinizarin) used inProcedures I and II was prepared as follows:

120 G (0.500 mole) of recrystallized 1,4-dihydroxyanthraquinone(quinizarin) was ground in a mortar and pestle with a small amount ofwater and transferred to a 5,000 m1 3- nec'k flask. Then water was addedto a total amount of 2,500 ml of water. After adding 120 g (1.130 mole)of sodium carbonate, the mixture was heated to 75 C under nitrogen. Then240 g 1.38 mole) of sodium hydrosulfite was added gradually within 1hour while stirring at 75 to 80 C under an atmosphere of nitrogen. Theresulting yellow suspension was stirred for 3 hours at. 75 to 80 C undera nitrogen atmosphere. This yellow suspension was filtered while hot (78C) and then washed with a solution containing 2.0 g of sodiumhydrosulfite in 4000 ml of water until neutral to litmus. The product(wet weight 203 g) was dried at room temperature under a high vacuum(0.05 mm of Hg). The vacuum dried product gave 108.0 g (0.446 mole) ofyellow solid with m. p. l52l54 C equivalent .to 89.2 percent of thetheoretical quantity of 2,3-dihydro- 1 ,4-dihydroxyanthraquinone.Recrystallization of 1.00 g from 100 ml of absolute ethyl alcoholproduced 0.60 g of yellow needles with m. p. l5415 5 C while a secondrecrystallization gave 0.40 g of yellow needles with m. p. 154-155 C.

ANALYSIS: Calculated for Found: C=69. l 8% H=4.29%

The starting material, 1,4-dihydroxyanthraquinone (quinizarin), waspurified by recrystallizing 200 g of commercial material from 4000 ml ofacetic acid to give 144 g of orange crystals with m.p. 196"-l97.5 C ofpurified 1,4-dihydroxyanthraquinone.

EXAMPLE 2 The procedure of Example 1 was followed except thathydrochloric acid was added to obtain a pH of 8.0. When applied to humanwhite hair, the composition produced medium golden brown color.

EXAMPLE 3 The procedure of Example 1 was followed except that sufficienthydrochloric acid was added to produce a pH of 6.5. When applied tohuman white hair, a dark brown color was obtained.

EXAMPLE 4 The procedure of Example 1 was followed except thathydrochloric acid was added to produce a pH of 4.0. When the compositionwas applied to human white hair, a light golden brown was obtained.

EXAMPLE 5 A mixture was prepared with the following ingredients:

The mixture had a pH of 9. 5. When applied to human white hair the colorwas dark bluish charcoal grey.

EXAMPLE 6 The procedure of Example 5 was followed except thathydrochloric acid was added to obtain a pH of 8. When applied to humanwhite hair a dark bluish charcoal grey color was obtained. 1

EXAMPLE 7 EXAMPLE 8 The procedure of Example 5 was followed except thathydrochloric acid was added to obtain a pH of 4.0. When applied to humanwhite hair, a medium golden brown was obtained.

EXAMPLE 9 A mixture was prepared with the following ingredients:

Ingredients Parts by Weight Active Dye A 1.00 2-nitro-p-phenylenediamine0.07 4-nitro m-phenylenediamine 0.07 Hydroxyethylcellulose, 4000 cps.1.00 Sodium benzoate 0.10 Citric Acid q.s. pH 6.5Isooctylphenylpolyethoxyethanol 2.00 lsopropyl Alcohol 10.00 Water q.s.

When applied to human white hair, a dark greyish brownwas obtained.

EXAMPLE 10 A mixture was prepared with the following ingredients:

Active Dye A 1.00 2-nitro-p-phenylenediamine 0.074-nitrorn-phenylenediamine 0.07 Hydroxyethylcellulose, 4000 cps. 1.00Sodium benzoate 0.10 Citric acid q.s. pH 6.5 Polyoxyethylene 10) oleylether 5.00 lsopropyl alcohol 10.00 Water q.s. 100% When applied to humanwhite hair, a medium brown was ob 4-nitro-m-phenylenediamine 0.07Hydroxyethylcellulose, 4000 cps. 0.50

Lactic acid q.s. pH 6.5 Polyoxyethylene ether of oleyl alcohol (20) 2.00Sodium bcnzoate 0.01 lsopropyl alcohol 10.00

Water q.s. 100% When applied to human white hair, a dark ash brown wasobtaincd.

EXAMPLE 13 The procedure of Example 12 was followed except that lacticacid was added to obtain a pH of 4.5.

When applied to human white hair, a medium golden brown was obtained.

EXAMPLES 14 THROUGH 39 Mixtures of ingredients of compositions wereprepared containing Active Dye A, a surfactant, a thickening agent andan acid or basic agent, if required. For each composition, the

quantity of Active Dye A, the identity and percent by weight Sufficienthydrochloric acid was added to obtain a pH of 7.0.

When applied to white human hair, a purplish blue color was obtained.

The active Dye B which is 6-( Z-methylaminoethylamino) 4- methyl-1,2,3,4-tetrahydronaphtho-[ 2,3-f]-quinoxaline-7, l 2- dione may beprepared by the following method:

9.68 G (0.040 mole) of 2,3-dihydro-1,4-dihydroxyanthraquinone(leucoquinizarin) was added gradually to 59.3 g (0.800 mole) ofN-methylethylenediamine while stirring under nitrogen. There was anexothermic reaction which raised, the temperature spontaneously from to40 C. A transient blue color developed and then a dark yellow-browncolor formed in the resulting thick suspension. The mixture was stirredfor 10 minutes at to C without heating to insure that the exotherm haddissipated. The reaction was heated in 20 minutes to C. The deepyellow-brown reaction mixture was stirred under nitrogen for 3 hours at50 to 52 C to effect the condensation reaction of leucoquinizarin with 2moles of the N-methylethylenediamine. It was then heated in 45 minutesto 100C. The reaction became a dark brown solution with a slightgreen'blue cast. It was stirred under nitrogen for another 3 hours at100 to 104 C in order Quantity in gins. 01 active Color on nat- Exampledye A Acid or basic agent Surfactant liy percent. Thickening agent bypercent p11 ural \vhit rt-air 14 0.2 Nitrilotriaectieaeid1.0polysorhate001.. 1.0enrlmxymethyl cellulose 4.5 Medium blu 15. 0. 2Boric acid 1.0 polyoxyethylene sorhitan 1.0 hydroxyethyl el-llulose 8. 0Dark blue.

monolaurate. 10. 0.2 Potassium nitrate 1.0 sodium laurylethersulfate"1.0 sodium ear-boxymethyl 1.0 l'ale blue.

cellulose. l7. (l. 2 'Iartaric aeid i 1.0 linoleie alkanolamide. 1.0earboxymethyl cellulose 4. 0 Light lolu 1X". 0.2 Sodium bicarbonate 1.0eoeonut alkanolnmide 1.0 hydroxyethyl eellulos g. Medium blu 10 0.2Ammonium chloride r i 1.0lsmmtylphenyl polyethoxyethdo s. 0 114;.

nnol. 20."... 0.2 Luetie acid. 1.0 polyoxyethylene (l0) olvyl 1.0 methylcellulose. 4. 0 Light blu ether. 21 0.2 1.0 oleieacid andphosphoricacidv 1.0 eoeonui. diethnnolamide .do. 4. 0 liarlr blu 12. 0.2 Diethanolamine 1.0 Nieoeo ll-nrnino propionie 1.0 eurhoxynu-l.l| vleellulose s. 8 Light blu aeu 0. .2 Monoethanolamine 1.0 N-laurylmyristyl ll-amlno 1.0 sodium earlioxymethyl 0. 2 lale blue.

proplonie arid. cellulose. 0.2 Monoisopropanol amine 1.0 1/2 salt ofsodium N-lauryl do 0. 0 1m.

B-iminodi propionic acid. 0. 2 Methyl morpholine 1.0 N c0e0 ll-aminopropionie 1.0 earhoxymethyl eellulos 7. 8 Light blue. 0. 2 N-ethylmorpholinc 1.0 N-lauryl myristyl li -amino do 7. 5 o.

propionic acid. 0. 2 Acetic acid 1.0 M sodium salt N-lauryl B- 1.0carboxymcthyl eellulosc. 4. 5 Do.

amino dipropionic acid. 0.2 Acetic acid 1.0 isoocytlphcnyl polycthoxy-..d0 4.5 Do.

ethanol. 0.2 Hydrochloric acid 1.0 Nlauryl fl-iminodi propionie ..do 4.5 D0.

are 0. 2 Acetic acid 1.0 isoocytlphcnyl p0lycthoxydo 4. 5 Do.

4 ethanol. 0. 2 llydrocliloilc acid 1.0 N-ilauryl B-iminodi propionie do4. s Do.

acu 0.18 Nitrilotriacctic acid 0.0 polysorhate do a. 0 Do. 0.10 lloricacid 1.0 polyoxyethylene sorhitun 1.0 hydroxyethyl cellulose i 8. 0Medium blu monolaurate. 0.10 Potassium nitrate 1.0 sodium lauryl ethersulfate. 1.0 sodium carlioxymethyl 0. 0 Pale blu cellulose. 0.10Tartarieaeid 1.0 linoleie alkanolamide 1.0 earboxymethyl cellulose 4. 0Light blu 0.1) Phosphoric acid sodium hicur- 1.0 coconut alkanolumide.1.0 hydroxyethyl cellulose" 7. 3 Do.

honate. 0.10 Ammonium chloridm... 1.0 isooetylplienyl-polyethoxy- ..,doi U H H k. 0 Dark blue.

ethanol. 0- 2 Lactic acid 1.0 polyoxyethylenfll0) oleyl 1.0 methylcellulose, Medium 1110"."

ether. 0. 2 (Hole acid 1.0 eoeonui. diethmiolimide do Light blue Adj.t0p11 7.5.

2 Adj. to p11 7.0N1I 01I.

Diluted 50/50 with (1% hydrogen peroxide. 4 Adj. to p11 0.5 Nllmll.

EXAMPLE 40 A mixture was prepared with the following ingredients:

6-( 2-methylaminoethylamino)-4-methy1- l,2,3,4-tetrahydronaphtho-[2,3-f]- quinoxaline-quinoxaline-7, l Z-dione (hereinafter called ActiveDye B") 0.5 Sodium laurylsulfate 1.0 Water 98 5 washed with two mlportions of N-methylethylenediamine. The bronzy crystals were washedwith 100 ml of anhydrous diethyl ether which removed some red impurity.The solid was ground in a mortar and pestle with 25 ml of methylalcohol. This suspension was filtered andthe solid washed with ml ofmethyl alcohol and dried. Some of the product dissolved in the methylalcohol. 1 A yield of 2.60 g (0.00743 mole) of crystalline solid wasobtained with m.p. l85l9l C, mostly l8919l C, equal to 18.6%oftheoretical yield of 6-( Z-methylaminoethylamino )-4- methyl-1,2,3,4-tetrahydtonaphtho-[2,3-f1-quinoxaline-7, dione. Thin layerchromatography showed only one strong blue component. Recrystallizationof this 2.60 g from a total of 100 ml of n-butyl alcohol gave 1.99. g(0.00568 mole) of blue crystals with metallic luster with m.p. 19,3-l94C equivalent to 14.20 percent of theoretical yield. A secondrecrystallization of 0.34 g from 75 ml of n-butyl alcohol gave 0.28 g ofcrystals with m.p l93194 C. ANALYSIS: Calcd for Foundi C=6 8.54%;H=6.32%; N=15.94%

The starting material 2,3-dihydro-l,4-dihydroxyanthraquinone(leucoquinizarin) was prepared as indicated under Example 1.

EXAMPLE 41 A mixture was prepared with the following ingredients:

6-(2-ethylaminoethylamino)-4-ethyl-1,2,3 ,4-

tetrahydronaphtho-[ 2 ,3-f] -quinoxaline-7, l 2- dione (hereinaftercalled Active Dye C") 0.5 Triton X-100 (isooctylphenyl polyethoxyethanol) 1.0 Water 98.5

0 IIN/ 011,

H I N O NlICllzCIIzNIICUzCllg A solution I containing 4.7 g (0.053 mole)of N- ethylethylenediamine in 18.5 ml of absolute alcohol was added froma dropping funnel into a stirred mixture of 3.7 g (0.015 mole) ofquinizarin, 0.8 g'(0.0075 mole) of sodium carbonate, 5.2 g (0.055 mole)of phenol and 12 ml of water.

The reaction was heated to reflux and stirred overnight at reflux underan atmosphere of nitrogen. The reaction mixture was then poured into asaturated sodium chloride solution. The product, which precipitated, wasthen collected and dissolved in acetone. This acetone solution of thedye was poured into another saturated sodium chloride solution. The dyewas extracted several times with ethyl acetate. The ethyl acetatesolution of the dye was dried over anhydrous magensium sulfate andfiltered. The ethyl acetate solution was evaporated to dryness. Theresidue, after evaporating the ethyl acetate, was dissolved in dilutehydrochloric acid and extracted with methylene chloride to remove someimpurities. The aqueous phase was made alkaline and extracted withmethylene chloride to remove the dye from the aqueous phase. Thismethylene chloride solution of the dye was evaporated to dryness and thedye recrystallized from methylcyclohexane. The magnesium sulfate used todry the original ethyl acetate extracts had absorbed some of the blue"dye. It was isolated from the magnesium sulfate by dissolving it inwater and extracting and recrystallizing as described above. Thecombined product was recrystallized a second time from methylcyclohexane to give 0.63 g, equivalent to 10.9 percent of thetheoretical yield of 6-( 2-ethylaminoethylamino )-4-ethyl- 1 ,2,3,4-tetrahydronaphtho-[2,3,-f]-quinoxaline-7,l2-dione as very dark bluecrystals with m.p. 1 19l 20 C.

EXAMPLE 42 A mixture was prepared with the followingingredients:

Active Dye C" 0.5

BTC 2125 [A mixture of equal quantities of n-alkyl dimethyl benzylammonium chlorides and nalkyl dimethyl ethyl benzyl ammonium chlorides.Each of the ammonium chlorides comprise a mixture containing varyingamounts of carbon atoms in the n-alkyl group. The

' mixture of n-alkyl dimethyl benzyl ammonium chlorides consists of 60%containing 14 carbon atoms in the n-alkyl group, 30% containing 16carbon atoms, 5% containing 12 carbon atoms and 5% containing 18 carbonatoms. The mixture of n-alkyl dimethyl ethyl benzyl ammonium chloridesconsists of 50% containing 12 carbon atoms in the n-alkyl group, 30%containing 14 carbon atoms, 17% containing 16 carbon atoms and 3%containing 18 carbon atoms.) 0.5

Water Sufficient hydrochloric acid is added to obtain a pH of 7.0.

When applied to white human hair, a medium blue color was obtained andwhen applied to damaged human hair, a blue-black color resulted.

EXAMPLE 43 A mixture was prepared with the following ingredients:

Active Dye A" 0.

Sodium lauryl sulfate Water When applied to white human hair, a darkblue color was obtained and when applied to damaged hair, a blue-blackcolor resulted.

EXAMPLE 44 When applied to white human hair, a dark blue color wasobtained and when applied to damaged hair, a blue-black color resulted.

EXAMPLE 45 A mixture was prepared with the following ingredients:

Active Dye A" 0.5 BTC 2125 0.5 Water 99.0

When applied to white human hair, a dark blue color was obtained andwhen applied to damaged hair, a blue-black color resulted.

EXAMPLE 46 A mixture was prepared with the following ingredients:

Active Dye 8" 0.5 Triton X-lOO 1.0 Water 98.5

When applied to white human hair, a dark blue color was obtained andwhen applied to damaged hair, a blue-black color resulted.

EXAMPLE 47 A mixture was prepared with the following ingredients:

Active Dye 8" 0.5 BTC 2125 0.5 Water 99.0 l00.0

' '1 ,2,3,4-tetrahydronaphtho-[2,3-f]-quinoxaline-7,12-dione;

and 6-(2-ethylaminoethylamino)-4-ethyl1,2,3 ,4-tetrahydronaphtho-[2,3-f]-quinoxaline-7,l2-dione and a surfactant.

2. A composition for dyeing human hair in accordance with claim 1 whichalso contains a thickening agent and an acidic or basic agent forcontrolling the pH of the composition.

3. A composition for dyeing human hair in accordance with claim 1 inwhich the surfactant is 0.1 to 10 percent and the thickening agent is0.1 to 10 percent.

4. A composition for dyeing human hair in accordance with claim 1 inwhich the surfactant is 0.2 to 5 percent and the thickening agent is 0.2to 5 percent.

5. A composition for dyeing human hair in accordancewith claim 1 inwhich the surfactant is 0.5 to 2 percent and the thickening agent is 0.5to 2 percent.

6. A composition for dyeing human hair in accordance with claim 1 inwhich said member is 6-( 2-aminoethylamino)-l,2,3,4-tetra.hydronaphtho-[2,3-f]-quinoxaline-7, l Z-dione.

7. A composition for dyeing human hair in accordance with claim 1 inwhich said member is 6-( 2- methylaminoethyamino)-4-methyll ,2,3 ,4-tetrahydronaphtho-[ 2,3-f] -quinoxaline-7,12-dione.

8. A composition for dyeing human hair in accordance with claim 1 inwhich said member is 6-( Z-ethylaminoethylamino 4-ethyl-l ,2,3,4-tetrahydronaphtho-[ 2 ,3-t] -quinoxaline-7 ,l 2-

2. A composition for dyeing human hair in accordance with claim 1 whichalso contains a thickening agent and an acidic or basic agent forcontrolling the pH of the composition.
 3. A composition for dyeing humanhair in accordance with claim 1 in which the surfactant is 0.1 to 10percent and the thickening agent is 0.1 to 10 percent.
 4. A compositionfor dyeing human hair in accordance with claim 1 in which the surfactantis 0.2 to 5 percent and the thickening agent is 0.2 to 5 percent.
 5. Acomposition for dyeing human hair in accordance with claim 1 in whichthe surfactant is 0.5 to 2 percent and the thickening agent is 0.5 to 2percent.
 6. A composition for dyeing human hair in accordance with claim1 in which said member is6-(2-aminoethylamino)-1,2,3,4-tetrahydronaphtho-(2,3-f)-quinoxaline-7,12-dione.
 7. A composition for dyeing human hair in accordance with claim1 in which said member is 6-(2-methylaminoethyamino)-4-methyl-1,2,3,4-tetrahydronaphtho-(2,3-f)-quinoxaline-7,12-dione.
 8. A compositionfor dyeing human hair in accordance with claim 1 in which said member is6-(2-ethylaminoethylamino)-4-ethyl-1,2,3,4-tetrahydronaphtho-(2,3-f)-quinoxaline-7,12-dione.